Nonvolatile variable resistance element

ABSTRACT

According to one embodiment, a nonvolatile variable resistance element includes a first electrode, a second electrode, a variable resistance layer, and a dielectric layer. The second electrode includes a metal element. The variable resistance layer is arranged between the first electrode and the second electrode. A resistance change is reversibly possible in the variable resistance layer according to move the metal element in and out. The dielectric layer is inserted between the second electrode and the variable resistance layer and has a diffusion coefficient of the metal element smaller than that of the variable resistance layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of PCT international application Ser.No. PCT/JP2011/076598 filed on Nov. 11, 2011 which designates the UnitedStates and claims the benefit of priority from Japanese PatentApplication No. 2011-032875 filed on Feb. 18, 2011; the entire contentsof which are incorporated herein by reference.

FIELD

Embodiments described herein relate generally to a nonvolatile variableresistance element.

BACKGROUND

In recent years, the development of a two-terminal nonvolatile variableresistance element represented by a ReRAM (Resistive Random AccessMemory) is actively performed. In the nonvolatile variable resistanceelement, a low-voltage operation, high-speed switching, and scaling downare possible. Therefore, the nonvolatile variable resistance element isprospective as a next-generation large capacity storage device thatreplaces an existing product such as a floating gate type NAND flashmemory. Specifically, examples of the nonvolatile variable resistanceelement include a nonvolatile variable resistance element in whichamorphous silicon is used as a variable resistance layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a first embodiment.

FIG. 2A is a sectional view of a low resistance state of the nonvolatilevariable resistance element shown in FIG. 1 and FIG. 2B is a sectionalview of a high resistance state of the nonvolatile variable resistanceelement shown in FIG. 1.

FIG. 3 is a graph of a switching characteristic of the nonvolatilevariable resistance element shown in FIG. 1.

FIG. 4 is a graph of the switching characteristic of the nonvolatilevariable resistance element shown in FIG. 1 compared with a switchingcharacteristic of a nonvolatile variable resistance element notincluding a dielectric layer.

FIG. 5 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a third embodiment.

FIG. 6A is a sectional view of a low resistance state of the nonvolatilevariable resistance element shown in FIG. 5 and FIG. 6B is a sectionalview of a high resistance state of the nonvolatile variable resistanceelement shown in FIG. 5.

FIGS. 7A and 7B are energy band charts of a generation process for aconductive filament of the nonvolatile variable resistance element shownin FIG. 5.

FIG. 8 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a fifth embodiment.

FIG. 9A is a sectional view of a low resistance state of the nonvolatilevariable resistance element shown in FIG. 8 and FIG. 9B is a sectionalview of a high resistance state of the nonvolatile variable resistanceelement shown in FIG. 8.

FIG. 10A is a plan view of a schematic configuration of a memory cellarray to which a nonvolatile variable resistance element according to asixth embodiment is applied and FIG. 10B is a sectional view of aschematic configuration of a cross point section of the memory cellarray shown in FIG. 10A.

FIG. 11 is a plan view for explaining a voltage setting method duringwriting in a selected cell in the memory cell array shown in FIG. 10A.

FIG. 12 is a plan view for explaining a voltage setting method duringreadout from the selected cell in the memory cell array shown in FIG.10A.

FIG. 13 is a plan view for explaining a voltage setting method duringerasing of the selected cell in the memory cell array shown in FIG. 10A.

FIG. 14 is a sectional view of a schematic configuration of anonvolatile variable resistance element according to a seventhembodiment.

FIG. 15 is a plan view of a schematic configuration of a memory cellarray to which the nonvolatile variable resistance element shown in FIG.14 is applied.

FIG. 16 is a sectional view of a schematic configuration of anonvolatile variable resistance element according to an eighthembodiment.

FIG. 17 is a plan view of a schematic configuration of a memory cellarray to which the nonvolatile variable resistance element shown in FIG.16 is applied.

DETAILED DESCRIPTION

In general, according to one embodiment, a nonvolatile variableresistance element includes a first electrode, a second electrode, avariable resistance layer, and a dielectric layer. The second electrodeincludes a metal element. The variable resistance layer is arrangedbetween the first electrode and the second electrode. A resistancechange is reversibly possible in the variable resistance layer accordingto move the metal element in and out. The dielectric layer is insertedbetween the second electrode and the variable resistance layer and has adiffusion coefficient of the metal element smaller than that of thevariable resistance layer.

Exemplary embodiments of the nonvolatile variable resistance elementwill be explained below in detail with reference to the accompanyingdrawings. The present invention is not limited to the followingembodiments.

First Embodiment

FIG. 1 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a first embodiment.

In FIG. 1, in this nonvolatile variable resistance element, a variableresistance layer 2 is laminated on a first electrode 1. A secondelectrode 4 is laminated on the variable resistance layer 2 via adielectric layer 3.

The variable resistance layer 2 includes semiconductor elements. Thesemiconductor elements can be selected out of, for example, Si, Ge,SiGe, GaAs, InP, GaP, GaInAsP, GaN, and SiC. The variable resistancelayer 2 can be an amorphous semiconductor, can be a polycrystallinesemiconductor, or can be a monocrystalline semiconductor. For example,polycrystal silicon, amorphous silicon, or monocrystal silicon can beused. N or O can be added to the semiconductor element. For example, thesemiconductor element can be SiN or SiO₂. The film thickness of thevariable resistance layer 2 is typically 1 nanometer to 300 nanometers.If microminiaturization of elements is taken into account, the filmthickness is desirably smaller. However, if the film thickness is toosmall, a uniform film is not formed. Therefore, the film thickness ismore desirably 2 nanometers to 50 nanometers.

When the semiconductor element of the variable resistance layer 2 is Si,impurity-doped silicon can be used as the first electrode 1. Forexample, high-density B, As, or P ions can be injected into silicon suchthat the resistivity of the first electrode 1 is equal to or smallerthan 0.005 Ωcm.

The second electrode 4 includes metal elements. As the metal elements,for example, Ag can be used. As the first electrode 1 and the secondelectrode 4, a conductive material other than Ag can be used. Forexample, as the first electrode 1 and the second electrode 4, Ag, Au,Ti, Ni, Co, Al, Fe, Cr, Cu, Hf, Pt, Ru, Zr, Bi or Ir, a nitride or acarbide of the metal, a chalcogenide material, or the like can be used.Further, an alloy material containing a plurality of metals orsemiconductor elements among such metals or semiconductor elements canbe used as the first electrode 1 and the second electrode 4. The firstelectrode 1 and the second electrode 4 can include the same metal.However, the first electrode 1 is desirably formed of a material that isless easily ionized than the second electrode 4.

The dielectric layer 3 has a smaller diffusion coefficient of the metalelements included in the second electrode 4 than in the variableresistance layer 2. The dielectric layer 3 can be selected out of, forexample, a silicon oxide film, a silicon nitride film, an oxynitride,and a carbide. The material and the film thickness of the dielectriclayer 3 are desirably set such that ions of the metal elements includedin the second electrode 4 can pass through the dielectric layer 3. Inother words, if the dielectric layer 3 is uniformly present between thevariable resistance layer 2 and the second electrode 4, the filmthickness of the dielectric layer 3 is desirably smaller. The filmthickness of the dielectric layer 3 can be set to 5 nanometers or less.The dielectric constant of the dielectric layer 3 is desirably smallerthan that of the variable resistance layer 2.

This nonvolatile variable resistance element changes from a highresistance state to a low resistance state when a conductive filament,which is formed of the metal elements supplied from the second electrode4, is formed in the variable resistance layer 2. The nonvolatilevariable resistance element changes from the low resistance state to thehigh resistance state when metal elements of the conductive filamentformed in the variable resistance layer 2 are collected in the secondelectrode 4 and the conductive filament formed in the variableresistance layer 2 are reduced in size.

In the variable resistance layer 2, a resistance change is reversiblypossible according to supply and collection of the metal elementsincluded in the second electrode 4. When the nonvolatile variableresistance element changes from the high resistance state to the lowresistance state, the metal elements of the second electrode 4 areionized to enter the variable resistance layer 2. The ionized metalelements combine with electrons, whereby the conductive filament isformed in the variable resistance layer 2. When the nonvolatile variableresistance element changes from the low resistance state to the highresistance state, holes are supplied to the variable resistance layer 2via the first electrode 1, whereby the metal elements of the conductivefilament are ionized. The ionized metal elements are collected in thesecond electrode 4, whereby the conductive filament in the variableresistance layer 2 is extinguished.

The dielectric layer 3 is provided between the variable resistance layer2 and the second electrode 4. This makes it possible to suppress themetal elements of the second electrode 4 from diffusing to the variableresistance layer 2. Therefore, even when the conductive filament in thevariable resistance layer 2 is extinguished, it is possible to preventthe metal elements of the second electrode 4 from remaining oozing outinto the variable resistance layer 2 and suppress deterioration ininsulation properties of the variable resistance layer 2. Therefore, itis possible to realize a reduction in the film thickness of the variableresistance layer 2 and reduce a driving current of the nonvolatilevariable resistance element. It is possible to microminiaturize thenonvolatile variable resistance element and realize an increase in thecapacity of a memory. Further, it is possible to improve an ON/OFF ratioof an electric current flowing to the nonvolatile variable resistanceelement and improve reliability.

It is desirable that an electric current more easily flows to thedielectric layer 3 than to the variable resistance layer 2. This isbecause, if the dielectric layer 3 has better insulation properties andhigher resistance than the variable resistance layer 2, a switchingaction in the variable resistance layer 2 does not occur. By setting thefilm thickness and the dielectric constant of the dielectric layer 3smaller than those of the variable resistance layer 2, it is possible toallow an electric current to more easily flow to the dielectric layer 3than to the variable resistance layer 2.

FIG. 2A is a sectional view of the low resistance state of thenonvolatile variable resistance element shown in FIG. 1. FIG. 2B is asectional view of the high resistance state of the nonvolatile variableresistance element shown in FIG. 1.

In FIG. 2A, in a generation process for a conductive filament F1, thepotential of the second electrode 4 is set to be higher than thepotential of the first electrode 1 to apply a set voltage to the secondelectrode 4.

When the set voltage is applied to the second electrode 4, the metalelements of the second electrode 4 are ionized. The ionized metalelements enter the variable resistance layer 2 via the dielectric layer3 and electrons are supplied to the variable resistance layer 2 via thefirst electrode 1. In the variable resistance layer 2, the ionized metalelements and the electrons combine, whereby the conductive filament F1formed of the metal elements included in the second electrode 4 growsinto the variable resistance layer 2.

The conductive filament F1 formed of the metal elements of the secondelectrode 4 grows into the variable resistance layer 2 and the firstelectrode 1 and the second electrode 4 are short-circuited by theconductive filament F1, whereby the nonvolatile variable resistanceelement is set in the low resistance state.

On the other hand, as shown in FIG. 2B, in an extinction process for theconductive filament F1, the potential of the second electrode 4 is setto be lower than the potential of the first electrode 1 to apply a resetvoltage to the second electrode 4.

When the reset voltage is applied to the second electrode 4, holes aresupplied to the variable resistance layer 2 via the first electrode 1,whereby metal elements 5 of the conductive filament F1 are ionized inthe variable resistance layer 2. The metal elements 5 of the conductivefilament F1 are collected in the second electrode 4 via the dielectriclayer 3 and the conductive filament F1 is extinguished in the variableresistance layer 2, whereby the nonvolatile variable resistance elementis reset to the high resistance state.

Reversible control of the low resistance state and the high resistancestate can be performed according to the polarity of voltage application.At this point, the high resistance state can be associated with an OFFstate and the low resistance state can be associated with an ON state. Acurrent value flowing to the nonvolatile variable resistance elementwhen a certain voltage is applied is read to distinguish the ON stateand the OFF state. This makes it possible to cause the nonvolatilevariable resistance element to operate as a memory. Because transitionof the high resistance state and the low resistance state occurs onlyduring voltage application, it is possible to realize a nonvolatilememory.

FIG. 3 is a graph of a switching characteristic of the nonvolatilevariable resistance element shown in FIG. 1.

In FIG. 3, when a voltage applied to the second electrode 4 of thenonvolatile variable resistance element is increased in the positivedirection (P1), an electric current suddenly increases at a set voltageVset (near 4 volts) and the nonvolatile variable resistance elementtransitions from the high resistance state to the low resistance state.

In the low resistance state, in a range in which the voltage applied tothe second electrode 4 is smaller than the set voltage Vset to someextent, the electric current flows generally in proportion to thevoltage (P2).

On the other hand, when the voltage applied to the second electrode 4 isswept in the negative direction with respect to the nonvolatile variableresistance element in the low resistance state, the electric currentsuddenly decreases at a reset voltage Vreset (near −2.5 volts) and thenonvolatile variable resistance element transitions from the lowresistance state to the high resistance state (P3).

In the high resistance state, in a range in which the voltage applied tothe second electrode 4 is larger than the reset voltage Vreset to someextent, the electric current hardly flows with respect to the voltage(P4).

When the voltage applied to the second electrode 4 is further swept inthe positive direction from this state (P1), the electric currentsuddenly increases at the set voltage Vset and the nonvolatile variableresistance element transitions from the high resistance state to the lowresistance state. In other words, the nonvolatile variable resistanceelement reversibly transitions between the high resistance state and thelow resistance state and can store data for one bit.

FIG. 4 is a graph of the switching characteristic of the nonvolatilevariable resistance element shown in FIG. 1 compared with a switchingcharacteristic of a nonvolatile variable resistance element notincluding a dielectric layer. L1 indicates a switching characteristicobtained when the dielectric layer 3 is present. L2 indicates aswitching characteristic obtained when the dielectric layer 3 is absent.

In FIG. 4, between the absence and the presence of the dielectric layer3, a difference in a voltage at which the transition from the highresistance state to the low resistance state occurs when a positivevoltage is applied to the second electrode 4, i.e., a so-called setvoltage Vset is a difference equal to or smaller than 1 volt. Thevoltage does not substantially vary.

However, the magnitude of an OFF current, which is an electric currentflowing during the high resistance state, is smaller by one digit whenthe dielectric layer 3 is present compared with the magnitude of the OFFcurrent flowing when the dielectric layer 3 is absent. On the otherhand, the magnitude of an ON current, which is an electric currentflowing during the low resistance state is about the same as themagnitude of the ON current flowing when the dielectric layer 3 isabsent. In other words, it is seen that an effect of reducing the OFFcurrent is improved by inserting the dielectric layer 3.

Second Embodiment

A method of manufacturing a nonvolatile variable resistance elementaccording to a second embodiment is explained. In an example explainedin the second embodiment, p-type Si, amorphous silicon, a silicon oxidefilm, and silver Ag are respectively used as the first electrode 1, thevariable resistance layer 2, the dielectric layer 3, and the secondelectrode 4 shown in FIG. 1.

For example, a p-type Si region formed by injecting B ions into asilicon monocrystal substrate under conditions that an accelerationvoltage is 30 keV and a dosage is 2×10¹⁵ cm⁻² and thereafter applyingactivation anneal to the silicon monocrystal substrate is formed as thefirst electrode 1.

Subsequently, an amorphous silicon layer is deposited as the variableresistance layer 2 by, for example, the chemical vapor deposition (CVD).In this embodiment, the LP-CVD (Low Pressure Chemical Vapor Deposition)is used.

After a natural oxide film is removed by fluoric acid treatment of thesurface of the amorphous silicon layer, SH treatment (cleaning by mixedliquid of sulfuric acid: hydrogen peroxide solution=2:1) is performed toform a chemical oxide film (SiO_(x)) of about 2 nanometer as thedielectric layer 3.

An Ag layer is vapor-deposited on the dielectric layer 3 as the secondelectrode 4. This makes it possible to manufacture the nonvolatilevariable resistance element shown in FIG. 1.

Third Embodiment

FIG. 5 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a third embodiment.

In FIG. 5, in this nonvolatile variable resistance element, a variableresistance layer 12 is laminated on a first electrode 11. A secondelectrode 14 is laminated on the variable resistance layer 12 via ahydroxide layer 13.

The first electrode 11, the variable resistance layer 12, and the secondelectrode 14 are the same as the first electrode 1, the variableresistance layer 2, and the second electrode 4 shown in FIG. 1.

The hydroxide layer 13 includes a hydroxide of metal elements of thesecond electrode 14. The hydroxide layer 13 can be selected out of, forexample, AgOH, Mg(OH)₂, Fe(OH)₂, Zn(OH)₂, Al(OH)₃, and Cu(OH)₂ accordingto the metal elements of the second electrode 14.

The nonvolatile variable resistance element changes from a highresistance state to a low resistance state when a conductive filament,which is formed of the metal elements supplied from the second electrode14, is formed in the variable resistance layer 12. The nonvolatilevariable resistance element changes from the low resistance state to thehigh resistance state when metal elements of the conductive filamentformed in the variable resistance layer 12 are collected in the secondelectrode 14 and the conductive filament formed in the variableresistance layer 12 is reduced in size.

In the variable resistance layer 12, a resistance change is reversiblypossible according to supply and collection of the metal elementsincluded in the second electrode 14. At this point, the metal elementsof the second electrode 14 are ionized to enter the variable resistancelayer 12. The ionized metal elements combine with electrons, whereby theconductive filament is formed in the variable resistance layer 12. Holesare supplied to the variable resistance layer 12 via the first electrode11, whereby the metal elements of the conductive filament are ionized.The ionized metal elements are collected in the second electrode 14,whereby the conductive filament in the variable resistance layer 12 isextinguished.

The hydroxide layer 13 is provided between the variable resistance layer12 and the second electrode 14. This makes it possible to promoteionization of the metal elements of the second electrode 14 on aninterface with the hydroxide layer 13. It is possible to reduce avoltage necessary for changing the resistance of the variable resistancelayer 12 and reduce a working current.

FIG. 6A is a sectional view of the low resistance state of thenonvolatile variable resistance element shown in FIG. 5. FIG. 6B is asectional view of the high resistance state of the nonvolatile variableresistance element shown in FIG. 5.

In FIG. 6A, in a generation process for a conductive filament F2, thepotential of the second electrode 14 is set to be higher than thepotential of the first electrode 11 to apply a set voltage to the secondelectrode 14.

On the interface of the hydroxide layer 13, an OH radical of thehydroxide layer 13 acts on the metal elements of the second electrode14, whereby the ionization of the metal elements of the second electrode14 is promoted. The ionized metal elements enter the variable resistancelayer 12 and electrons are supplied to the variable resistance layer 12via the first electrode 11. In the variable resistance layer 12, theionized metal elements and the electrons combine, whereby the conductivefilament F2 formed of the metal elements of the second electrode 14grows into the variable resistance layer 12.

The conductive filament F2 formed of the metal elements of the secondelectrode 14 grows into the variable resistance layer 12 and the firstelectrode 11 and the second electrode 14 are short-circuited by theconductive filament F2, whereby the nonvolatile variable resistanceelement is set in the low resistance state.

On the other hand, as shown in FIG. 6B, in an extinction process for theconductive filament F2, the potential of the second electrode 14 is setto be lower than the potential of the first electrode 11 to apply areset voltage to the second electrode 14.

Holes are supplied to the variable resistance layer 12 via the firstelectrode 11, whereby metal elements 15 of the conductive filament F2are ionized in the variable resistance layer 12. At this point, the OHradical of the hydroxide layer 13 is moved to the variable resistancelayer 12 by an electric field and acts on the metal elements 15 of theconductive filament F2, whereby the ionization of the metal elements 15of the conductive filament F2 is promoted. The metal elements 15 of theconductive filament F2 are collected in the second electrode 14 and theconductive filament F2 is extinguished in the variable resistance layer12, whereby the nonvolatile variable resistance element is reset to thehigh resistance state.

FIGS. 7A and 7B are energy band charts of a generation process for theconductive filament of the nonvolatile variable resistance element shownin FIG. 5. In an example shown in FIGS. 7A and 7B, p-type Si, amorphoussilicon, an AgOH film, and silver Ag are respectively used as the firstelectrode 11, the variable resistance layer 12, the hydroxide layer 13,and the second electrode 14 shown in FIG. 5.

In FIG. 7A, the OH radical of the hydroxide layer 13 acts on silver Agof the second electrode 14, whereby a reaction described below occursand silver Ag of the second electrode 14 is hydrogenated.

Ag+OH⁻→AgOH+e⁻

Because a hydroxide of silver Ag is unstable, a reaction described belowoccurs, whereby silver Ag is ionized and supplied to the variableresistance layer 12.

AgOH

Ag⁺+OH⁻

As shown in FIG. 7B, an electron e⁻ is supplied to the variableresistance layer 12 via the first electrode 11 and a silver ion Ag⁺ andthe electron e⁻ combine, whereby the conductive filament F2 formed ofsilver Ag grows in the variable resistance layer 12.

In this way, when the hydroxide of the electrode metal is present, metalions are generated by the reaction of the hydroxide and the ionizationof the electrode metal is promoted. This reaction is not a reactionpeculiar to silver Ag and could occur in other metals such as copper Cu.

Fourth Embodiment

A method of manufacturing a nonvolatile variable resistance elementaccording to a fourth embodiment is explained. In an example explainedin the fourth embodiment, p-type Si, amorphous silicon, an AgOH film,and silver Ag are respectively used as the first electrode 11, thevariable resistance layer 12, the hydroxide layer 13, and the secondelectrode 14 shown in FIG. 5.

For example, a p-type Si region formed by injecting B ions into asilicon monocrystal substrate under conditions that an accelerationvoltage is 30 keV and a dosage is 2×10¹⁵ cm⁻² and thereafter applyingactivation anneal to the silicon monocrystal substrate is formed as thefirst electrode 11.

Subsequently, an amorphous silicon layer is deposited as the variableresistance layer 12 by, for example, the chemical vapor deposition(CVD).

After a natural oxide film is removed by fluoric acid treatment of thesurface of the amorphous silicon layer, SH treatment is performed toOH-terminate the surface of the amorphous silicon layer.

An Ag layer is vapor-deposited as the second electrode 14 and an OHradical on the surface of the amorphous silicon layer and Ag of thesecond electrode 14 are caused to react, whereby the hydroxide layer 13is inserted between the second electrode 14 and the variable resistancelayer 12.

In the example explained the embodiments explained above, the electrodesand the layers are laminated in the order of the first electrode 11, thevariable resistance layer 12, the hydroxide layer 13, and the secondelectrode 14. However, the electrodes and the layers can be laminated inthe order of the second electrode 14, the hydroxide layer 13, thevariable resistance layer 12, and the first electrode 11. In this case,when an Ag layer is used as the second electrode 14, it is possible toform AgOH on the surface of the Ag layer by performing SH treatment ofthe Ag layer.

However, when AgOH on the surface of the Ag layer is put in anenvironment in which AgOH is unstable and is immediately decomposed, toallow AgOH to be easily formed, the SH treatment can be performed aftera layer including the OH radical is formed on the Ag layer.

For example, it is possible to, after forming the Ag layer, laminate anamorphous silicon layer of about 1 nanometer or less, OH-terminate thesurface of the amorphous silicon layer through the SH treatment of theamorphous silicon layer, and form the variable resistance layer 12 onthe surface of the amorphous silicon layer. At this point, it ispossible to insert the hydroxide layer 13 between the second electrode14 and the variable resistance layer 12 by causing the OH radical on thesurface of the amorphous silicon layer and Ag of the second electrode 14to react.

Fifth Embodiment

FIG. 8 is a sectional view of a schematic configuration of a nonvolatilevariable resistance element according to a fifth embodiment.

In FIG. 8, in this nonvolatile variable resistance element, a variableresistance layer 22 is laminated on a first electrode 21. A secondelectrode 25 is laminated on the variable resistance layer 22sequentially via a dielectric layer 23 and a hydroxide layer 24.

The first electrode 21, the variable resistance layer 22, the dielectriclayer 23, and the second electrode 24 are the same as the firstelectrode 1, the variable resistance layer 2, the dielectric layer 3,and the second electrode 4 shown in FIG. 1. The hydroxide layer 24 isthe same as the hydroxide layer 13 shown in FIG. 5.

The nonvolatile variable resistance element changes from a highresistance state to a low resistance state when a conductive filament,which is formed of the metal elements supplied from the second electrode25, is formed in the variable resistance layer 22. The nonvolatilevariable resistance element changes from the low resistance state to thehigh resistance state when metal elements of the conductive filamentformed in the variable resistance layer 22 are collected in the secondelectrode 25 and the conductive filament formed in the variableresistance layer 22 is reduced in size.

In the variable resistance layer 22, a resistance change is reversiblypossible according to supply and collection of the metal elementsincluded in the second electrode 25. At this point, the metal elementsof the second electrode 25 are ionized to enter the variable resistancelayer 22. The ionized metal elements combine with electrons, whereby theconductive filament is formed in the variable resistance layer 22. Holesare supplied to the variable resistance layer 22 via the first electrode21, whereby metal elements of the conductive filament are ionized. Theionized metal elements are collected in the second electrode 25, wherebythe conductive filament in the variable resistance layer 22 isextinguished.

The dielectric layer 23 and the hydroxide layer 24 are provided betweenthe variable resistance layer 22 and the second electrode 25. This makesit possible to suppress the metal elements of the second electrode 25from diffusing to the variable resistance layer 22 and promoteionization of the metal elements of the second electrode 25 on aninterface with the hydroxide layer 24. Therefore, it is possible tosuppress deterioration in insulation properties of the variableresistance layer 22. Further, it is possible to improve an ON/OFF ratioof an electric current flowing to the nonvolatile variable resistanceelement and reduce a voltage and a working current necessary forchanging the resistance of the variable resistance layer 22.

FIG. 9A is a sectional view of the low resistance state of thenonvolatile variable resistance element shown in FIG. 8. FIG. 9B is asectional view of the high resistance state of the nonvolatile variableresistance element shown in FIG. 8.

In FIG. 9A, in a generation process for a conductive filament F3, thepotential of the second electrode 25 is set to be higher than thepotential of the first electrode 21 to apply a set voltage to the secondelectrode 25.

On the interface of the hydroxide layer 24, an OH radical of thehydroxide layer 24 acts on the metal elements of the second electrode25, whereby the ionization of the metal elements of the second electrode25 is promoted. The ionized metal elements enter the variable resistancelayer 22 via the dielectric layer 23 and electrons are supplied to thevariable resistance layer 22 via the first electrode 21. In the variableresistance layer 22, the ionized metal elements and the electronscombine, whereby the conductive filament F3 formed of the metal elementsof the second electrode 25 grows into the variable resistance layer 22.

The conductive filament F3 formed of the metal elements of the secondelectrode 25 grows into the variable resistance layer 22 and the firstelectrode 21 and the second electrode 25 are short-circuited by theconductive filament F3, whereby the nonvolatile variable resistanceelement is set in the low resistance state.

On the other hand, as shown in FIG. 9B, in an extinction process for theconductive filament F3, the potential of the second electrode 25 is setto be lower than the potential of the first electrode 21 to apply areset voltage to the second electrode 25.

Holes are supplied to the variable resistance layer 22 via the firstelectrode 21, whereby metal elements 26 of the conductive filament F3are ionized in the variable resistance layer 22. At this point, the OHradical of the hydroxide layer 24 is moved to the variable resistancelayer 22 by an electric field and acts on the metal elements 26 of theconductive filament F3, whereby the ionization of the metal elements 26of the conductive filament F3 is promoted. The metal elements 26 of theconductive filament F3 are collected in the second electrode 25 via thedielectric layer 23 and the conductive filament F3 is extinguished inthe variable resistance layer 22, whereby the nonvolatile variableresistance element is reset to the high resistance state. (SixthEmbodiment)

FIG. 10A is a plan view of a schematic configuration of a memory cellarray to which a nonvolatile variable resistance element according to asixth embodiment is applied. FIG. 10B is a sectional view of a schematicconfiguration of a cross point section of the memory cell array shown inFIG. 10A.

In FIGS. 10A and 10B, in a memory cell array 30, lower wires 31 areformed in a column direction and upper wires 34 are formed in a rowdirection. A nonvolatile variable resistance element 33 is arranged in across point section between the lower wire 31 and the upper wire 34 viaa rectifying element 32. As the nonvolatile variable resistance element33, for example, the nonvolatile variable resistance element shown inFIG. 1, FIG. 5, or FIG. 8 can be used. In an example shown in FIG. 10B,a method of providing the rectifying element 32 on the nonvolatilevariable resistance element 33 is explained. However, the rectifyingelement 32 can be removed.

FIG. 11 is a plan view for explaining a voltage setting method duringwriting in a selected cell in the memory cell array shown in FIG. 10A.

In FIG. 11, around the memory cell array 30, a control unit 35 thatperforms row selection and a control unit 36 that performs columnselection are provided. When writing in a selected cell is performed,the set voltage Vset is applied to the lower wire 31 of a selectedcolumn and a half voltage of the set voltage Vset is applied to thelower wires 31 of unselected columns. 0 volt is applied to the upperwire 34 of a selected row and the half voltage of the set voltage Vsetis applied to the upper wires 34 of unselected rows.

As a result, the set voltage Vset is applied to the selected celldesignated by the selected column and the selected row and writing inthe selected cell is performed.

The half voltage of the set voltage Vset is applied to half-selectedcells designated by the unselected columns and the selected row andwriting in the half-selected cells is prohibited. The half voltage ofthe set voltage Vset is applied to half-selected cell designated by theselected column and the unselected rows and writing in the half-selectedcells is prohibited. 0 volt is applied to unselected cells designated bythe unselected columns and the unselected rows and writing in theunselected cells is prohibited.

FIG. 12 is a plan view for explaining a voltage setting method duringreadout from a selected cell in the memory cell array shown in FIG. 10A.

In FIG. 12, when readout from the selected cell is performed, a halfvoltage of a read voltage Vread is applied to the lower wire 31 of aselected column and 0 volt is applied to the lower wires 31 ofunselected columns. A minus half voltage of the read voltage Vread isapplied to the upper wire 34 of a selected row and 0 volt is applied tothe upper wires 34 of unselected rows.

As a result, the read voltage Vread is applied to the selected celldesignated by the selected column and the selected row and readout fromthe selected cell is performed. On the other hand, the minus halfvoltage of the read voltage Vread is applied to half-selected cellsdesignated by the unselected columns and the selected row and readoutfrom the half-selected cells is prohibited. The half voltage of the readvoltage Vread is applied to half-selected cells designated by theselected column and the unselected rows and readout from thehalf-selected cells is prohibited. 0 volt is applied to unselected cellsdesignated by the unselected columns and the unselected rows and readoutfrom the unselected cells is prohibited.

FIG. 13 is a plan view for explaining a voltage setting method duringerasing of a selected cell in the memory cell array shown in FIG. 10A.

In FIG. 13, when erasing of the selected cell is performed, the resetvoltage Vreset is applied to the lower wire 31 of a selected column anda half voltage of the reset voltage Vreset is applied to the lower wire31 of unselected columns. 0 volt is applied to the upper wire 34 of aselected row and the half voltage of the reset voltage Vreset is appliedto the upper wires 34 of unselected rows.

As a result, the reset voltage Vreset is applied to the selected celldesignated by the selected column and the selected row and erasing ofthe selected cell is performed. On the other hand, the half voltage ofthe reset voltage Vreset is applied to half-selected cells designated bythe unselected columns and the selected row and erasing of thehalf-selected cells is prohibited. The half voltage of the reset voltageVreset is applied to half-selected cells designated by the selectedcolumn and the unselected rows and erasing of the half-selected cells isprohibited. 0 volt is applied to unselected cells designated by theunselected columns and the unselected rows and erasing of the unselectedcells is prohibited.

Seventh Embodiment

FIG. 14 is a sectional view of a schematic configuration of anonvolatile variable resistance element according to a seventhembodiment.

In FIG. 14, a gate electrode 45 is formed on a semiconductor substrate41 via a gate insulating film 44. A word line 46 is formed on the gateelectrode 45. In the semiconductor substrate 41, impurity diffusionlayers 42 and 43 are formed to hold a channel region formed under thegate electrode 45, whereby a transistor 51 is formed. A source line 47is connected to the impurity diffusion layer 43.

On the semiconductor substrate 41, the nonvolatile variable resistanceelement 33 is arranged adjacent to the transistor 51. As the nonvolatilevariable resistance element 33, for example, a configuration same asthat shown in FIG. 1 can be used. The second electrode 4 of thenonvolatile variable resistance element 33 is connected to the impuritydiffusion layer 42 via a connection conductor 48. The first electrode 11of the nonvolatile variable resistance element 33 is connected to a bitline 50 via a connection conductor 49.

The transistor 51 is turned on via the word line 46, whereby thenonvolatile variable resistance element 33 can be accessed and thenonvolatile variable resistance element 33 set as a read and writetarget can be selected.

In the explanation of an example shown in FIG. 14, the configurationshown in FIG. 1 is used as the nonvolatile variable resistance element33. However, the configuration shown in FIG. 5 or FIG. 8 can be used.

FIG. 15 is a plan view of a schematic configuration of a memory cellarray to which the nonvolatile variable resistance element shown in FIG.14 is applied.

In FIG. 15, on the semiconductor substrate 41 shown in FIG. 14, bitlines BL1 to BL3 are wired in a column direction and word lines WL1 toWL3 are wired in a row direction. In cross point sections of the bitlines BL1 to BL3 and the word lines WL1 to WL3, nonvolatile variableresistance elements 33 and transistors 51 are arranged. The nonvolatilevariable resistance elements 33 and the transistors 51 are connected inseries to each other.

One ends of the nonvolatile variable resistance elements 33 of the samecolumns are connected to the same bit lines BL1 to BL3. One ends of thetransistors 51 of the same rows are connected to the same source linesSL1 to SL3. Gate electrodes 45 of the transistors 51 of the same rowsare connected to the same word lines WL1 to WL3.

The transistors 51 are turned on via the word lines WL1 to WL3, wherebya voltage can be applied between first electrodes 1 and secondelectrodes 4 of the nonvolatile variable resistance elements 3 of aselected row. Therefore, during readout from the nonvolatile variableresistance elements 33 of the selected row, it is possible to prevent anelectric current from flowing to the nonvolatile variable resistanceelements 33 of the unselected rows and reduce readout time.

Eight Embodiment

FIG. 16 is a sectional view of a schematic configuration of anonvolatile variable resistance element according to an eighthembodiment.

In FIG. 16, the nonvolatile variable resistance element 33 is arrangedon a lower wire 61. A unipolar variable resistance element 67 isarranged on the nonvolatile variable resistance element 33 via aconnection conductor 62. An upper wire 66 is arranged on the unipolarvariable resistance element 67. In the unipolar variable resistanceelement 67, a variable resistance layer 64 is laminated on a lowerelectrode 63 and an upper electrode 65 is laminated on the variableresistance layer 64. As the variable resistance layer 64, a transitionmetal oxide such as HfO₂, ZrO₂, NiO, V₂O₅, ZnO, TiO₂, Nb₂O₅, WO₃, or CoOcan be used. In the unipolar variable resistance element 67, theresistance of the variable resistance layer 64 can be changed bychanging the amplitude and the time of pulse stress applied to thevariable resistance layer 64.

When forward bias is applied to the unipolar variable resistance element67, the set voltage Vset is applied to the nonvolatile variableresistance element 33 via the lower wire 61. This makes it possible toform the conductive filament F1 shown in FIG. 2A in the variableresistance layer 2 and reduce the resistance of the nonvolatile variableresistance element 33.

On the other hand, when reverse bias is applied to the unipolar variableresistance element 67, the reset voltage Vreset is applied to thenonvolatile variable resistance element 33 via the lower wire 61. Thismakes it possible to extinguish the conductive filament F1 shown in FIG.2A from the variable resistance layer 2 and increase the resistance ofthe nonvolatile variable resistance element 33.

The nonvolatile variable resistance element 33 is connected to theunipolar variable resistance element 67 in series. This makes itpossible to improve an ON/OFF ratio compared with an ON/OFF ratioobtained when a diode is connected to the unipolar variable resistanceelement 67 in series.

In the explanation of an example shown in FIG. 16, the configurationshown in FIG. 1 is used as the nonvolatile variable resistance element33. However, the configuration shown in FIG. 5 or FIG. 8 can be used.

FIG. 17 is a plan view of a schematic configuration of a memory cellarray to which the nonvolatile variable resistance element shown in FIG.16 is applied.

In FIG. 17, the bit lines BL1 to BL3 are wired in a column direction andthe word lines WL1 to WL3 are wired in a row direction. In cross pointsections of the bit lines BL1 to BL3 and the word lines WL1 to WL3, thenonvolatile variable resistance elements 33 and unipolar variableresistance elements 67 are arranged. The nonvolatile variable resistanceelements 33 and the unipolar variable resistance elements 67 areconnected in series to each other.

One ends of the unipolar variable resistance elements 67 of the samecolumns are connected to the same bit lines BL1 to BL3. One ends of thenonvolatile variable resistance elements 33 of the same rows areconnected to the same word lines WL1 to WL3.

According to such connection, when reverse bias is applied to unselectedcells, the resistance of the variable resistance elements is increased.Therefore, it is possible to reduce current noise flowing from theunselected cells during current readout from a selected cell, improvestability of a readout operation, and reduce a readout time.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel embodiments described hereinmay be embodied in a variety of other forms; furthermore, variousomissions, substitutions and changes in the form of the embodimentsdescribed herein may be made without departing from the spirit of theinventions. The accompanying claims and their equivalents are intendedto cover such forms or modifications as would fall within the scope andspirit of the inventions.

What is claimed is:
 1. A nonvolatile variable resistance elementcomprising: a first electrode; a second electrode including a metalelement; a variable resistance layer arranged between the firstelectrode and the second electrode, a resistance change being reversiblypossible in the variable resistance layer according to move the metalelement in and out, and the variable resistance layer having asemiconductor element; and a dielectric layer inserted between thesecond electrode and the variable resistance layer, the dielectric layerhaving a diffusion coefficient of the metal element smaller than that ofthe variable resistance layer.
 2. The nonvolatile variable resistanceelement according to claim 1, wherein the variable resistance layer ispolycrystal silicon, amorphous silicon, or monocrystal silicon.
 3. Thenonvolatile variable resistance element according to claim 1, whereinthe dielectric layer is a silicon oxide film, a silicon nitride film, anoxynitride film, or a carbide film.
 4. The nonvolatile variableresistance element according to claim 1, wherein the first electrode isimpurity-doped silicon.
 5. The nonvolatile variable resistance elementaccording to claim 1, wherein the metal element is selected out of Ag,Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta, Au, Bi and Zr.
 6. A nonvolatilevariable resistance element comprising: a first electrode; a secondelectrode including a metal element; a variable resistance layerarranged between the first electrode and the second electrode, aresistance change being reversibly possible in the variable resistancelayer according to move the metal element in and out, and the variableresistance layer having a semiconductor element; and an insulating filminserted between the second electrode and the variable resistance layerand selected out of a group including a silicon oxide film, a siliconnitride film, an oxynitride film, and a carbide film.
 7. The nonvolatilevariable resistance element according to claim 2, wherein the variableresistance layer is polycrystal silicon, amorphous silicon, ormonocrystal silicon.
 8. The nonvolatile variable resistance elementaccording to claim 6, wherein the first electrode is impurity-dopedsilicon.
 9. The nonvolatile variable resistance element according toclaim 6, wherein the metal element is selected out of Ag, Ti, Ni, Co,Al, Cr, Cu, W, Hf, Ta, Au, Bi and Zr.
 10. The nonvolatile variableresistance element according to claim 6, wherein a laminated structureof the first electrode, the variable resistance layer, the dielectriclayer, and the second electrode is arranged at a cross point of a wordline and a bit line.
 11. The nonvolatile variable resistance elementaccording to claim 10, further comprising a rectifying element arrangedbetween the word line and the bit line.
 12. The nonvolatile variableresistance element according to claim 6, further comprising a transistorconnected to the laminated structure in series.
 13. A nonvolatilevariable resistance element comprising: a first electrode; a secondelectrode including a metal element; a variable resistance layerarranged between the first electrode and the second electrode having asemiconductor element; and a hydroxide layer inserted between the secondelectrode and the variable resistance layer, the hydroxide layer havinga hydroxide of the metal element.
 14. The nonvolatile variableresistance element according to claim 11, wherein the variableresistance layer is polycrystal silicon, amorphous silicon, ormonocrystal silicon.
 15. The nonvolatile variable resistance elementaccording to claim 13, wherein the hydroxide layer is selected out ofAgOH, Mg(OH)₂, Fe(OH)₂, Zn(OH)₂, Al(OH)₃, and Cu(OH)₂.
 16. Thenonvolatile variable resistance element according to claim 13, whereinthe first electrode is impurity-doped silicon.
 17. The nonvolatilevariable resistance element according to claim 13, wherein the metalelement is selected out of Ag, Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta, Au, Biand Zr.
 18. The nonvolatile variable resistance element according toclaim 13, wherein a laminated structure of the first electrode, thevariable resistance layer, the dielectric layer, and the secondelectrode is arranged at a cross point of a word line and a bit line.19. The nonvolatile variable resistance element according to claim 18,further comprising a rectifying element arranged between the word lineand the bit line.
 20. A nonvolatile variable resistance elementcomprising: a first electrode; a second electrode including Ag; avariable resistance layer arranged between the first electrode and thesecond electrode and having a semiconductor element; and a silverhydroxide layer inserted between the second electrode and the variableresistance layer.
 21. The nonvolatile variable resistance elementaccording to claim 20, wherein the variable resistance layer ispolycrystal silicon, amorphous silicon, or monocrystal silicon.
 22. Thenonvolatile variable resistance element according to claim 20, whereinthe first electrode is impurity-doped silicon.
 23. The nonvolatilevariable resistance element according to claim 20, wherein a laminatedstructure of the first electrode, the variable resistance layer, thesilver hydroxide layer, and the second electrode is arranged at a crosspoint of a word line and a bit line.
 24. The nonvolatile variableresistance element according to claim 23, further comprising arectifying element arranged between the word line and the bit line. 25.A nonvolatile variable resistance element comprising: a first electrode;a second electrode including Cu; a variable resistance layer arrangedbetween the first electrode and the second electrode and having asemiconductor element; and a copper hydroxide layer inserted between thesecond electrode and the variable resistance layer.
 26. The nonvolatilevariable resistance element according to claim 25, wherein the variableresistance layer is polycrystal silicon, amorphous silicon, ormonocrystal silicon.
 27. The nonvolatile variable resistance elementaccording to claim 25, wherein the first electrode is impurity-dopedsilicon.
 28. The nonvolatile variable resistance element according toclaim 25, wherein a laminated structure of the first electrode, thevariable resistance layer, the copper hydroxide layer, and the secondelectrode is arranged at a cross point of a word line and a bit line.29. The nonvolatile variable resistance element according to claim 28,further comprising a rectifying element arranged between the word lineand the bit line.